Hoxchi



United States Patent PROCESS FOR DYEING OR PRINTING CELLU- LOSE-CONTAINING MATERIALS AND DYE- STUFF PREPARATIONS THEREFOR Karl Menzi and Jacques Wegmann, Basel, Switzerland, gsslgnors to Ciba Limited, Basel, Switzerland, a Swiss No Drawing. Application November 10, 1952, Serial No. 319,773

Claims priority, application Switzerland November 16, 1951 18 Claims. (Cl. 8-42) The present invention is based on the observation that cellulose-containing materials can be dyed or printed with great advantage by using a neutral to alkaline dyebath or printing paste which contains a dyestufl containing at least two azo-linkages and capable of forming complex metal compounds sparingly soluble in water, an amine, advantageously an aliphatic amine, which contains at least one amino group separated by two carbon atoms from an HO-group, phosphorus-containing anions of a phosphoric acid containing at least two phosphorus atoms in the acid molecule, especially a phosphoric acid of the constitution in which m represents a whole number greater than 1, and an alkali-resistant compound of a metal having an atomic number from 27 to 29, advantageously one in which the metal is bound to at least one of the aforesaid substances.

It will be understood from the foregoing that there may be used for preparing the dyebath either the finished complex metal compounds or mixtures capable of forming them.

In the latter case there is used, for example, a neutral to alkaline dyebath or printing paste for the preparation of which there are used an amine, advantageously an aliphatic amine, which contains at least one amino group separated by two carbon atoms from an HO-group, phosphorus-containing anions of a phosphoric acid containing at least two phosphorus atoms in the acid molecule, especially an acid of the constitution there is used an amine, advantageously an aliphatic amine,

containing at least one amino group separated by two carbon atoms from an HO-group, a phosphorus compound of a phosphoric acid containing at least two phosphorus atoms in the acid molecule, and especially an acid of the constitution Hm+2PmO3m+l in which m represents a whole number greater than 1, and a sparingly soluble complex metal compound of a dyestuif containing at least two azo linkages, of which the metal in complex union is a metal having an atomic number from 27 to 29.

I The dyebaths can generally be prepared either directly in the concentration necessary for dyeing or advantagearias? Patented June 5, 1956 ice ously by diluting so-called stock solutions, which have the compositions given above, but contain the aforesaid ingredients in a higher concentration usually too great for dyeing.

The dyestuifs used for preparing the printing pastes or solutions may, as stated above be used in the form of their complex metal compounds of metals having an atomic number from 27 to 29, or free from metal in complex union together with an alkali-resistant agent yielding such a metal. As metals there come into consideration cobalt or especially nickel or copper, and above all the latter. As alkali-resistant agents yielding metal there are to be understood metal compounds which are not converted into their hydroxides in alkaline solutions, such as are customary in the usual direct dyeing methods, but which are capable of metallizing dyestuffs.

The dyestuifs contain at least two azo linkages and at least one group capable of forming complexes, and are sparingly soluble in water in the form of their cobalt, nickel or copper complexes, and are therefore unsuitable for dyeing by the usual direct dyeing methods.

The dyestuffs may contain as metallized or metallizable groups, for example, ortho:ortho'-dihydroxy-azo-grouplogs or ortho-hydroxy-ortho'-carboxy-azo-groupings, and, if desired, may contain metallized or metallizable groups diiferent from each other. Especially valuable results are obtained with dyestuffs which contain as a metallizable or metallized group an ortho-hydroxyaryl-ortho-carboxyazo-grouping or an ortho:ortho-dihydroxy-azo-grouping having at least one hydroxyl group bound to an aryl carbon atom.

The dyestuffs and their complex cobalt, nickel or copper compounds coming into consideration may be made by methods in themselves known. A large number of suitable dyestuifs of the kind defined above, especially those free from metal, is known. Among the latter dyestuifs there may be used in the manner described above practically all those which as such or in the form of their cobalt, nickel or copper complexes yield sparingly soluble metal compounds, but which can be used for dyeing cellulose fibers by the known after-metallizing processes.

For the preparation of the solutions or printing pastes to be used in the invention it is of advantage that the ionogenic acid groups present in the dyestulfs, that is to say especially sulfonic acid and carboxylic acid groups (insofar as the latter are not to take part in the formation of complexes), should be in the form of their alkali metal salts.

The amines, advantageously aliphatic amines, used in the process of the invention contain at least one amino group which is separated by two carbon atoms from an HO-group, which latter group may be present in a carboxylic acid group. The amines are therefore characterized by the presence of at least one atomic grouping of the formula HO K As examples there may be mentioned monoethanolamine, aminoacetic acid, fi-hydroxyethylaminoacetic acid, and 2- amino-1-hydroxybenzene-4-sulfonamide.

In many cases, as will be understood from the foregoing, there may be used solid amines, for example, those melting above 50 C. There have been found advantageous, for example, the amines of the constitution in which R1 represents a hydrogen atom, an alkyl group having at most 3 carbon atoms or a hydroxymethyl group, R2 represents a hydrogen atom or a methyl group, and n represents a whole number not greater than 4, and advantageously 2.

As examples the amines of the following constitution may be mentioned:

Especially valuable results are obtained with 1:2-di- (fi-hydroxyethylamino)-ethane of the formula Melting point 93 to 94 C.

The phosphorus compounds present in the solutions used for dyeing or printing in accordance with the invention are derived from polyphosphoric acids. There may be used, for example, compounds derived from pyrophosphoric acid or higher polyphosphoric acids such as HsPaOw or HeP4013.

With regard to the relative proportions of the substances described above, which are present in the solutions or are used for preparing the solutions, the following remarks should be noted: When metal-free dyestuffs are used for preparing the solutions it is desirable to add the theoretical quantity of the agent yielding metal or slightly more than that quantity. It is also advisable to introduce more than 2 molecules of the aliphatic amine per group capable of forming complexes. of the phosphorus-containing anion may vary Within wide limits. Thus, good results are obtained when the proportion by weight of pyrophosphate or polyphosphate ions amounts to about one-sixth of the proportion of dyestutf, but even greater quantities have no disadvantageous effect. It is of advantage in practice to use a proportion of phosphorus-containing ions amounting to about one-third to twice the weight of the dyestuif.

The solutions and printing pastes may be prepared in different ways, of which a few especially advantageous methods are described below. Generally, it is of advantage for preparing printing pastes, and also for preparing solutions to be used for dyeing, especially in the case of stock solutions, to use hot water. The following substances, for example, may be used for preparing the solutions or printing pastes:

(a) Complex metal compound of the dyestuff, aliphatic amine and alkali pyrophosphate (Na4PzO1) or an alkali polyphosphate,

(b) Complex metal compound of the dyestutf, pyrophosphate or polyphosphate of the amine and an alkali hydroxide or an excess of the amine,

(c) Metal-free dyestutf, complex metal compound of the amine, and alkali pyrophosphate or an alkali polyphosphate,

The quantity (d) Metal-free dyestutf, amine and alkali copper pyrophosphate (for example 3Na4P2O1+Cu2P2Oi),

(e) Metal-free dyestutf and the reaction product of copper pyrophosphate (CU2P2Q7 with the amine,

(f) Metal-free dyestutt, alkali pyrophosphate or an alkali polyphosphate, amine and alkali-resistant agent yielding copper, for example, a complex alkali-copper compound of an aliphatic hydroxycarboxylic acid such as lactic acid, citric acid or especially tartaric acid.

It will be understood that in the above compositions the terms dyestufi" and amine refer to the products as defined in the opening part of this specification.

The order of succession in which the ingredients mentioned under (a) to (f) are added to the water is generally quite optional and has no influence on the result. On the other hand, good results are usually impaired if, in preparing the solutions, other electrolytes are added in appreciable amounts to the ingredients specified, so that it is of advantage to avoid such further additions. For this reason it is desirable not to add the dyestufl, whether it be the metal-free or metalliferous product, in a form made up to a certain strength with sodium sulfate or sodium chloride, but to add it in the form in which it is usually separated out in the course of manufacture, and in which such salts are not present in quantities which would have a disadvantageous effect. This disadvantageous effect consists mainly in a disturbance of the process of dissolution, which at high dilutions, for example, at the concentration customary in dyebaths scarcely arises, but at high concentrations such, for example, as in stock solutions, printing pastes or the concentrations sometimes necessary in machine dyeing, may lead to the dyestufl being incompletely dissolved.

The dyebaths used in the process of the invention are neutral or advantageously alkaline solutions. Insofar as the alkaline reaction is not produced directly, for example, by the addition of a polyphosphatc or the presence of a suflicient proportion of amine, the alkaline reaction can be produced by adding suitable substances of alkaline reaction such as an alkali hydroxide, ammonia or further amine. For the reasons given above, however, it is generally not recommended to use alkali carbonates or bicarbonates for this purpose.

Instead of preparing the dyebaths, stock solutions or printing pastes by taking up the substances mentioned under (a) to (f) individually and successively in water, it is generally of advantage, where possible. to dry the ingredients or to work them up into preparations of paste form. Thus, for example, the substances gtiwtl under ((1) to (f) may be mixed together in the dry state or aqueous mixtures or solutions thereof may he prepared and, if desired, the latter may be evaporated to dryness.

As some of the amines used in the process of the invention are liquid and some of the solid amines have a strong hygroscopic action in the preparations, it may be of advantage in order to produce uniform results when such amines are used not to mix the amine with the solid preparation, but only to add the amine when thc solutions or printing pastes are to be prepared. Tor making up preparations of this kind there are numerous pus-nbilities which will be easily understood from those at the foregoing definitions of the dyebaths ttCc-in'diug to which a free amine is used (see also the various possibilities ((1 1 to (1) above). Thus, for example, those preparations have been found to be of value which contain a sparingly soluble complex cobalt, copper or nickel compound of a dyestutt' containing at least two azo linkages and an alkali pyrophosphate.

When the preparation, whether it contains the amine or not, is to be made up to a certain dyeing strength it is advisable for this purpose to select a larger or smaller quantity of the alkali pyrophosphate or polyphosphate as required, insofar as the preparation contains such a pyrophosphate or polyphosphate, and where the phosphate ions have been added in another form (for example, in

the form of sodium copper pyrophosphate) to add also am By replacing the 1:2-di-(p-hydroxyrethylamiho)ethane alkali phosphate if necessary. Alkali phosphates of this by the same quantity of aminoacetic acid (glycocoll) a kind are convenient diluents for the preparations because similar result is obtained.

in contradistinction to the usual additions such as sodium sulfate, they have no disadvantageous effect and the pro- 5 portion in which they are used may vary within wide Equal parts of crystalline sodium pyrophosphate, urea limits. Instead of or in addition to the alkali phosphates, and the copper compound of the dyestufi of the formula H (I) O H H 0 Example 2 HgN SOlH H0 8" however, there may be used non-electrolytes, such as are mixed together. 1 part of the resulting dyestutf urea or water-soluble carbohydrates such as saccharose preparation is covered with 1 part of Z-amino-ethanol,

or d xt i and the mixture is boiled with 200 parts of water to form Dyeing or printing with the solutions of the invention an aqueous stock solution.

is carried out by methods in themselves known for direct For the purpose of dyeing, the stock solution is diluted dyeing dyestuffs. to 2000 parts by volume, and 100 parts of well wetted cot- In the production of printing pastes it is generally ton are entered at 50-60 C. The temperature is raised to advisable to add hydrotropic agents, especially urea. As the boil in the course of /2 hour while moving the goods. the complex metal compounds are sensitive to reducing Boiling is continued for one hour, and 2 portions of 15 agents, it is generally of advantage to avoid the use of parts of crystalline sodium sulfate are added, one after 5 thickening agents, such as British gum, having a prominutes and the other after 20 minutes. After rinsing and nounced reducing action, and to use vegetable mucilages drying the goods, there is obtained a blue dyeing of excelsuch as tragacanth thickening. In other respects the lent fastness to light and washing. printing can be carried out in known manner, by drying The same result is obtained by replacing the Z-aminothe prints, and then steaming and rinsing. Usually a ethanol by an aqueous solution of 1 part of one of the relatively short steaming period of about 10-20 minutes products of the formulae sutfices to bring about complete fixation of the prints. HO CHT CHT NH In this manner there are obtained dyeings and prints distinguished by their good color strength, purity of tint and good properties of fastness. Hi

In certain cases it may be of advantage to after-treat HOAJHPCHPNH dyeings or prints obtained by the present process with agents which enhance their properties of wet fastness. E: As products that improve the wet fastness properties of HO CH7 2}H NH dyeings there may be mentioned inter alia, the reaction 4 products of formaldehyde with compounds such as cyanamide, dicyandiamide, dicyandiamidine, melamine, and H1 the like. There also come into consideration after-treat- HO-CHT CH -NH ing agents made without formaldehyde. H8

The following examples illustrate the invention, the CH CH parts and percentages being by weight unless otherwise a stated, and the relationship of parts by weight to parts i- I by volume being the same as that of the kilogram to the liter- Example 1 I HO-CH C-NH 5 parts of the copper compound of the dyestutf of the 2- formula & I C

i HOOC OOOH (IH' coon o-orr I -q O-NH-C o-i3 N=N -o H=OHC N=NEC O-NH are intimately mixed in the form of a press cake having an a dry content of 20 per cent. with 2 parts of sodium pyro- 110.4311, phosphate and 2 parts of 1:Z-di-(,B-hydroxyethylamino)- CH I ethane, and the mixture is dried in vacuo at 40-50 C.

HO- H: +11;

A part of the resulting mixture is dissolved in 1000 parts of water, and then further diluted to 3000 parts by CH volume. Into the dyebathso prepared and having a HCPGH! temperature of 60 C. there are entered 100 parts of g dpreviously wetted cotton, and dyeing is carried on for one H hour, the temperature being raised to -95 C. in the course of 20 minutes and after /2 hour 30 parts of crys- Example 3 talline sodium sulfate being added. After rinsing and 183 parts of l-aminoethanol are heated to C. y g the Cotton, there. is Obtained a b nish a ge while stirring, and 99 parts of 1:2-dichlorethane are run dyeing of good fastness to washing and light. '7 in slowly while refluxing. When the addition is complete,

the mixture is maintained for /2 hour at 140-150 C., urea and crystalline sodium pyrophosphate are mixed toand then cooled to room temperature. 80 parts of finely gether.

ground Sodium hydroxide Suspended in 300 Parts of In order to prepare a clear stock solution, 1 part of the I1 01 are then added, and the f f is filteffid after stir above dyestuff preparation is covered with a solution of 1 ring for 2 hours to remove precipitated sodlum chloride. 5 part of 122 di (phydmxyethylamino)-cthanc i 3 pal-15 The filtrate, a yellowish oil, 18 a mixture consisting mainof watgr, and boiled with 200 parts of Water g gfi and For dyeing, the resulting stock solution is diluted with water to 2000 parts by volume, and 100 parts of prel.5 arts of the filtrate are boiled with 1 at of a P p r viously wetted cotton are entered at 50-60 C. The

dyestuff preparation consisting of equal parts of crystalline odium pyrophosphatg urca and the opper m -und temperature is raised to thfi in the course Of A hour of the dyestutf of the formula while moving the goods. Boiling is continued for a COOH E0 on Hoot]; HO N=N-N=N *N=N N=N@ OH H006 HO;S- \NH/ -SO5H AZOOH in 200 parts of water to form a clear stock solution. further hour, during which two portions of parts of For dyeing the stock solution is diluted with water to crystalline sodium sulfate are added one after 5 min- 2000 parts by volume, and 100 parts of previously wetted utes and the other after 20 minutes. After rinsing and cotton are entered at 50-60" C. The temperature is raised drying there is obtained a blue dyeing of excellent fastto the boil in the course of /2 hour While moving the ness to light and washing. goods. Boiling is continued for one hour, during which 2 The same success is obtained with a dyestuflf preparaportions of 15 parts of crystalline sodium sulfate are added, tion which contains, instead of the copper compound of one after 5 minutes and the other after 20 minutes. After the dyestuff of the above formula, the same quantity of rinsing and drying there is obtained a blue dyeing of good r h product b i d b coppering accompanied b d faStnBSS t0 light and Washillgmethylation in known manner from the product of cou- Sodium Pyrophosphate may be replaPed by sodlum pling in an alkaline medium 1 mol of tetrazotized 4:4" tripolyphosphate (NaslsQio) or hexa-sodiurn tetrapolydiamino 3:3, dimeth0Xy 1II, diphenyl and 2 mols of phosphate (NasPsOrs) with the same success. (B hydroxyethylamino) 5 hydroxynaphthalene 7 Example 4 sulfonic acid.

By replacing the copper compound, by the same quan- Equal parts of the copper compound of the dyestufi tity of the nickel compound of the aforesaid dyestuff of the formula HOOC COOH H0 (HI 11000 OOH HO;S \NH sons h h d there is obtained a dyeing of a somewhat more reddish Crystalline so mm pyrop osp ate an ammoace 10 am tint, and also having very good fastness to light and washare mixed together. ing

2 parts of the resulting dyestuff preparation are dissolved in 400 parts of water. The resulting clear stock solution is diluted to 2000 parts by volume, and 100 parts v 0.5 part of the copper compound of the dyestutt' of of previously \vetted cotton are entered at 50-60" C. The the formula Example 6 00011 HO OH E000 E000 H0|S- \NH/ s0,H OOH temperature is raised to the boil in the course of /2 hour is boiled in 200 parts of water with 5 parts of sodium while moving the goods, Boiling i ontinued for o e hydroxide solution of 10 per cent. strength and the neuhour, during which 2 portions of 15 parts of crystalline tfal py phosphat 0f 1I2-d1-(fi-hydroxyethylammo)- sodium sulfate are added, one after 5 minutes and the ethane of the formula other after 20 minutes. After rinsing and drying there is obtained a blue dyeing of good fastness to light and wash- 2)2NH(CHz)zOH] P2O ing. v to form a clear stock solution.

Example 5 For dyeing, the stock solution is diluted with water to Equal parts of the copper compound of the dyestufi of 2000 Parts y Volume and Parts Of Pfcviously vetted the formula cotton are entered at 50-60 C. The temperature is 7 A- B0 on no HO-GHg-OHr-HN nms NH-CHr-CBr-OH 9 1 r raised to the boil in the course of /2 hour while moving By replacing in the aforesaid dyestufl' preparation, the the goods. Boiling is continued for 1 hour, during which copper compound by an'equal quantity of the cobalt comtwo portions of parts of crystalline sodium sulfate pound of the same dyestufi, there is obtained after dyeing are added one after 5 minutes and the other after a somewhat more greenish blue tint also of good fastness minutes. After rinsing and drying there is obtained a 5 to light and washing. blue dyeing of good fastness to light and washing. Example 9 The neutral pyrophosphate of lz2-di-(fl-hydroxyethylamino)-ethane is prepared as follows: 1 part of the dyestuff of the formula i coon H000 Z Won C-0H 0.-

17.8 parts of pyrophosphoric acid are dissolved in 200 is dissolved in 6000 pa of Water- 2 parts of sodium parts of water. l:Z-di-(B-dihydroxyethylamino)-ethane c pper pyrophosphate and 2 parts of 1: 2-di-(fi.hydroxyis added until the reaction is neutral to litmus, for which ethylamino)-ethane are then added. purpose 29.6 parts are required. The solution is evap- 20 The temperature of the resulting dyebath is brought to ()rated t d ss in vacuo. The new product is a yel- 60 C. and 200 parts of previously wetted cotton are l wax-like hygroscopic mass. entered. In the'c'ourse of /2 hour the temperature is Example 7 raised to 9095 C. After 20 minutes 60 parts of crystalline sodium sulfate are .added,- and then dyeing is carried on for a further /2 hour. At the end of this period Equal parts of the nickel compound of the dyestufi I the cotton is rinsed and dried, and there is obtained a of the formula OH no on HO HrN- S 03H H013 NHa brownish orange dyeing of good fastness to washing and saccharose and crystalline sodium pyrophosphate are mixed together. light. By using sodiumnickel pyrophosphate, instead of In order to prepare a clear stock solution'l part of sodium copper pyrophosphate, there is also obtained an the resulting dyestuff preparation is covered with a soorange dyeing.

lution of 1 part of 1:2-di- (B-hydroxyethylamino)-ethane By using sodium copper tartrate instead of sodium copin 3 parts of water, and boiled with 200 parts of water. per pyrophosphate there is obtained a duller and weaker For dyeing, the stock solution is diluted with'water to dyeing." 2000 parts, and 100 parts of previously wetted cotton are By using sodium copper pyrophosphate without 1:2-dientered at SO- C. The temperature is raised to the (fi-hydroxyethylamino)ethaneonly-a weak dyeing is boil in the course of /2 hour while moving the goods. tained.

By carrying out the above dyeing process in the absence of the base and copper pyrophosphate complex, and after- Boiling is continued for one hour, during which two portions of 15 parts of crystalline sodium sulfate are added one after 5 minutes and the other after 2.0 minutes. Aftcoopering in known manner there is obtained a dyeing er rinsing and drying there is obtained a blue dyeing that is weaker andduller, and corresponds somewhat to of excellent fastness to light and washing. the dyeing obtained in a single bath with the base and sodium copper tartrate.

Example 8 50 The sodium copper pyrophosphate 15 prepared inthe 1 part of the dyestuff preparation consist ng of equal following manner: parts of crystalline sodium pyrophosphate, urea and the 44.6 parts of crystalline sodium pyrophosphate are discopper compound of the dyestutf of the formula solved in 300 parts of hot water, and added to a solution Hoot: ([JOOH H? OH H000 v I Hots \NH -s 0.11 v 0011 is covered with a solution of 1 part of lz2-di-(fl-hydroxyof 51 parts of crystalline copper sulfate (CuSO4.SH2O) ethylam1no)-ethane 1n 3 parts of water, and the mixture in 200 parts .of water. There is formed immediately a is stirred. In order to obtain a clear stock solution the 5 white precipitate of copper pyrophosphate, which is mixture is boiled with 400 parts of water. filtered off and washed with water.

For dyemg, the stock solution is diluted with water to The resulting copper pyrophosphate is introduced into 2000 parts by volume and 100 parts of previously wetted a boiling solution of 134 parts of crystalline sodium pyrocotton are entered at 50-60 C. The temperature is phosphate in 150 parts of water; and the mixture is boiled ralsed to the boil in the course of /2 hour while moving untii dissolution is complete. The deep blue clear soluthe goods. Boiling is continued for one hour during tion is evaporated in vacuo, the easily water-soluble which two portions of 15 parts of crystalhne sodium sulsodium-copper pyrophosphate being precipitated in the fate are added one after 5 minutes and the other-after form of a pale powder. i

20 minutes. After IlIlSlDg and drying there is obtained In the same manner sodium nickel pyrophosphate can a blue dyeing of good fastness to light arid washing. b made f nickel sulfate;

is dissolved with 1 part of sodium hydroxide solution in Exam, 1e 400 parts of water. parts of the resulting stock solu- 1 part of the dyestuif of the formula tion are added to a dyebath of 280 parts of water at 60 H000 COOH HO OH 13000 COOH I l l l HOiS NH S 05H is dissolved in 100 parts of water. 50 parts of this stock C. 2 parts of a solution of 5 parts of sodium copper solution are added to 2900 parts of a dyebath having a pyrophosphate and 5 parts of 1:2-di-(fl-hydroxyethyltemperature of 60 C. After introducing 50 parts by amino)-ethane in 100 parts of water are then added, and volume of a solution of 1 part of sodium copper pyro- 16 100 parts of previously wetted cotton are entered.

phosphate and 2 parts of l:2-di-(B-hydroxyethylamino)- Dyeing is carried on for a total of one hour, the ethane in 100 Parts Wat6f."100 Parts Of pfevieusly temperature being raised slowly from about 50-60 C. wetted cotton are entered and dyeing is carried out as t 90 95 C, wh h b h i i ll h d, dfiscfibed in Example Thai? is Obtained a blue dyeing the cotton is rinsed and dried, and there is obtained a fast Washing and light; which is purer than: and of 20 greenish blue dyeing which is extraordinarily fast to the same strength as, a dyeing produced by the usual afterwashing and light cowering process' E l I] A dyeing produced with the same stock solution and B the same quantity of dyestutf, but by an ordinary after- 1 part of the dyestuff of the formula coppering process, is considerably weaker, even when and 1 part of sodium pyrophosphate are dissolved in parts of crystalline sodium sulfate are added to the 1000 parts of water and diluted to 3000 parts by volume. dyebath.

1 part of copper glycocoll [Cu(NH2CH2COO)2] By using instead of the above dyestuff, 1 part of the and 2 parts of l:Z-(fl-hydroxyethylamino)-ethane are then dyestutf of the formula H H ('i) (])H H moo-Gm; sons nois- NHC OCH1 added. 100 parts of cotton are dyed in the resulting bath and otherwise proceeding in the manner described above,

for one hour, the temperature being raised in the course there is produced a remarkably fast and strong blue of 20 minutes from 60 to 90-95 C., and after V2 hour 30 dyeing, which is stronger than a corresponding dyeparts of crystalline sodium sulfate are added. After exing produced by the usual after-coppering process. hausting the bath the dyeing is rinsed and dried. There is obtained a strong blue tint of very good fastness to Example 13 washing and light.

Similar results are obtained by using, instead of copper 4 parts of the dyestuff of the formula H rOJI glycocoll, sodium copper tartrate and, instead of 2 parts are mixed with 2 parts of sodium copper pyrophosphate of lzZ-di-(hydroxyethylamino)-ethane, 2 parts of monoand 1 part of glycocoll. ethanolamine. The mixture is introduced into a dyebath of 3000 By the usual methods of after-coppering there is obparts of water at C., and 100 parts of previously tained a more reddish duller tint of approximately the Wetted cotton are entered at the same tempera ur yesame strength. ing being carried on for a total of one hour. The

temperature is brought to the boil in the course of 20 minutes and after /2 hour 30 parts of crystalline sodium 1 part of the dyestuff of the formula sulfate are added.

Example I 2 011 HO on Gm s om V Y Ems Nil-O is M When the dyeing is complete, the goods are rinsed scribed above, there may be used with equal success the cold and dried, and there is obtained a yellow dyeing 551F116 q y of the Complex of the formula of very good fastness to washing and light, which is [Cu(HzNCHz-CH2OH)2]2P2O7 in no way inferior in strength and fastness to a cone It is prepared in a manner analogous to the prescripsponding dyeing produced by the known after-copperiug 5 tion given in the third to fifth paraghaphs of this exprocess. ample, 24.4 parts of Z-aminoethanol being used instead By using instead of glycocoll 2 parts of 1:2-di-(pof P3115 0f '(fi' y 'Q y y hydroxyethylamino)-ethane a similar good result is Example 15 obtained. 1 part of the dyestufl of the formula $00K HO OH H0O? Hood HOaS- S0|H OOH Example 14 is dissolved in 100 parts of water. 50 parts of the resulting stock solution is added to the dyebath and the 1 part Of he yestuff of the formula temperature is brought to 60 C. After introducing (300E (|)H OH 1100? H000 HOsS- \NH/ s 0,H boon is mixed with 1.5 parts of 1:2-di-(B-hydroxyethylamino)- 50 parts of a solution of 2 parts of sodium copper ethane and 1.4 parts of the copper pyrophosphate comtartrate and 2 parts of 1:2-di-(fl-hydroxyethylamino)- plex of the formula ethane and 1 part of crystalline sodium pyrophosphate [CU(HOCH2-CH2NHCHz-- in 100 parts of water, 100 parts of previously wetted CH2-NH-CH2-CH2--OH) lzPzo'z cotton are entered into the dyebath and dyeing is carried 1 part of th resulting dyestufif preparation i i on for a total of one hour, the temperature being raised solved at the boil in 200 parts of water. The resulting in the course f 20 minutes to and 3 pa ts clear solution is diluted with water to 2000 parts by of crystalline sodium sulfate being added after /2 hour. volume, and 100 parts of previously Wetted cotton are There is obtained a strong blue dyeing of very good fastentered at 60 C. The temperature is raised to the ness to light and washing. boil in the course of /2 hour while moving the goods. v Boiling is continued for an hour, during which two E l 16 portions of 15 parts of crystalline sodium sulfate are added, one after 5 minutes and the other after 20 minutes, 40 5 parts of the dyestufi of the formula After rinsing and drying the cotton, there is obtained are boiled with 10 parts of sodium copper pyro-phosphate a blue dyeing of good fastness to light and washing. (3Na4P2OmCu2P2O7), 10 parts of crystalline sodium pyro- The above-mentioned copper pyrophosphate complex phosphate and 150 parts of urea together with 30 parts is prepared as follows: of Z-aminoethanol in 305 parts of water. The mixture is A solution of 51 parts of crystalline copper sulfate in stirred into 500 parts of neutralized tragacanth thickening 200 parts of water added to a hot solution of 44.6 parts (/1000), and printed on cotton. After printing, the of crystalline sodium pyrophosphate in 300 parts of goods are dried and steamed for 10 minutes. After thor water. There is formed immediately a white precipi- 60 ough rinsing with cold Water, there is obtained a blue print tate of copper pyrophosphate, and the latter is filtered of ex ll nt fa tn to light and Washing, Ofi and Washed With Watef- Instead of the copper compound, there may be used The resulting Q PP PY P P is suspended in with equal success the same quantity of the nickel com- 500 parts of bOlllIlg Water and 29.6 parts of 1:2-d1-(B pound of the same dyestufi. hydroxyethylamino)-ethane are added, and the whole is boiled until a clear deep blue solution is obtained. Example 17 The solution is evaporated to dryness in vacuo, whereby a complex is obtained in the formv of a dark blue powder. 5 parts of the copper compound of the dyestuff of the Instead of the copper pyrophosphate complex deformula on OH on on HO.GH2.CH2.NH Ho's" are mixed with 15 parts of crystalline sodium pyrophosphate and 150 parts of urea, and boiled with 30 parts of a mixture consisting mainly of 1:2-di-(1S-hydroxyethylamino)-ethane and 2-aminoetharrol (prepared as described in Example 3) in 300 parts of water. The mixture is stirred into 500 parts of neutralized tragacanth thickening (60/1000) and printed on cotton. After printing, the goods are dried and steamed for minutes. After thoroughly rinsing in the cold there is obtained a blue print of excellent fastness to light and washing.

By using in this example, instead of the copper compound of the dyestufi, the same quantity of the nickel compound of the same dyestufi there are obtained somewhat more reddish prints having the same properties of fastness.

What we claim is:

1. Process for coloring cellulosic textile materials with metalliferous azo-dyestuffs sparingly soluble in water, which comprises applying to said materials a neutral to al kaline aqueous dyestuff composition which contains a dyestuff containing at least two azo linkages and being capable of forming metal compounds sparingly soluble in water, an aliphatic amine corresponding to the formula in which R1 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having at most three carbon atoms, and a hydroxymethyl group, R2 represents a member selected from the group consisting of a hydrogen atom and a methyl group, and n represents a whole number of at the most 4, and anions of a phosphoric acid containing at least two phosphorus atoms in the acid molecule, said composition containing in combined form a metal having an atomic number from 27 to 29, said metal being present in alkali-resistant combination.

2. Process for coloring cellulosic textile materials with metalliferous azo-dyestuffs sparingly soluble in water, which comprises applying to said materials a neutral to alkaline aqueous dyestuff composition which contains a dyestuif containing at least two azo linkages and being capable of forming metal compounds sparingly soluble in water, an aliphatic amine corresponding to the formula in which R1 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having at most three carbon atoms, and a hydroxymethyl group, R2 represents a member selected from the group consisting of a hydrogen atom and a methyl group, and n represents a whole number of at the most 4, and anions of a phosphoric acid corresponding to the formula in which in represents a whole number greater than 1, said composition containing in combined form a metal having an atomic number from 27 to 29, said metal being present in alkali-resistant combination.

3. Process for coloring cellulosic textile materials with mctalliferous azo-dyestuffs sparingly soluble in water, which comprises applying to said materials a neutral to alkaline aqueous dyestuff composition which contains a dyestuff containing at least two azo linkages and being capable of forming metal compounds sparingly soluble in water, an aliphatic amine corresponding to the formula R! CnHia=(-NH-(:3CHTOH) in which R1 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having at most three carbon atoms, and a hydroxymethyl group, R2 represents a member selected from the group consisting 16 of a hydrogen atom and a methyl group, and n represents a whole number of at the most 4, and anions of a phosphoric acid corresponding to the formula in which m represents a whole number greater than 1, said composition containing in combined form a metal having an atomic number from 28 to 29, said metal being present in alkali-resistant combination.

4. Process for coloring celulosic textile materials with metalliferous azo dyestuffs sparingly soluble in water, which comprises applying to said materials a neutral to alkaline aqueous dyestutf composition which contains dyestuff containing at least two azo linkages and being capable of forming metal compounds sparingly soluble in water, an aliphatic amine corresponding to the formula in which R1 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having at most three carbon atoms, and a hydroxymethyl group, R2 represents a member selected from the group consisting of a hydrogen atom and a methyl group, and n represents a whole number of at the most 4, and anions of pyrophosphoric acid, said composition containing in combined form a metal having an atomic number from 28 to 29, said metal being present in alkali-resistant combination.

5. Process for coloring cellulosic textile materials with metalliferous azo-dyestuffs sparingly soluble in water, which comprises applying to said materials a neutral to alkaline aqueous dyestuff composition which contains a dyestufi containing at least two azo linkages and being capable of forming metal compounds sparingly soluble in water, an aliphatic amine corresponding to the formula in which R1 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having at most three carbon atoms and a hydroxymethyl group, R2 represents a member selected from the group consisting of a hydrogen atom and a methyl group and n represents a Whole number of at the most 4, and anions of pyrophosphoric acid, said composition containing copper in combined form, said copper being present in alkali-resistant combination.

6. Process for coloring cellulosic textile materials with metalliferous azo-dyestuffs sparingly soluble in water, which comprises applying to said materials a neutral to alkaline aqueous dyestuif composition which contains a dyestufi containing at least two azo linkages and being capable of forming metal compounds sparingly soluble in water, an aliphatic amine corresponding to the formula in which R1 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having at most three carbon atoms and a hydroxymethyl group, R2 represents a member selected from the group consisting of a hydrogen atom and a methyl group and n represents a whole number of at the most 4, and anions of pyrophosphoric acid, said composition containing nickel in combined form, said nickel being present in alkali-resistant combination.

' 7. Process for coloring cellulosic textile materials with metalliferous azo dyestuffs sparingly soluble in water, which comprises applying to said materials a neutral to alkaline aqueous dyestuff composition which contains a dyestuff containing at least two azo linkages and being capable of forming metal compounds sparingly soluble in 17 1s water, 1:2-di-(p-hydroxyethylamino)-ethane, and anions of alkaline aqueous dyestufi composition which contains the pyrophosphoric acid, said composition containing copper complex copper compound of a dyestufi of the formula in combined form, said copper being present in alkali- HO OH resistant combination. I

8. Process for coloring cellulosic textile materials with 5 .R metalliferous azo dyestuffs sparingly soluble in water, which comprises pp y to Said materials a neutral to wherein each R represents the racial of a 2-amino-5- alkaline aqueous dyestufi composition Which Con a s a hydroxynaphthalene-7-sulfonic acid bound in 6-position dyestufi containing at least two azo linkages and being 1 h azo li k 1;2;di g h d thyl mino)- th capable of forming metal compounds sparingly soluble in 10 and an lk li pyrophgsphate,

Water, -(fiy y y and anions i2. Process for coloring cellulosic textile materials with of pyrophosphoric acid, Said Composition Containing metalliferous azo dyestuffs sparingly soluble in water, nickel in combined form, said nickel being pres nt in which comprises applying to said materials a neutral to alkali-resistant combination. alkaline aqueous dyestuif composition which contains the 9. Process for coloring cellulosic textile materials with lex nickel compound of a dyestutf of the formula metalliferous azo dyestuffs sparingly soluble in water, Ho OH which comprises applying to said materials a neutral to alkaline aqueous dyestufi composition which contains a dyestuff of the formula wherein each R represents the radical of a Z-amino-S- H0 I OH hydroxynaphthalene-7-sulfonic acid bound in 6-position I I to the azo linkage, l:2-di-(fi-hydroxyethylamino)ethane, RN=NON=NR and an alkali pyrophosphate.

13. Process for coloring cellulosic textile materials with metalliferous azo dyestuffs sparingly soluble in water, wherein each R represents the radical of a 2-amino-5-hy-, 'which comprises applying to said materials a neutral to droxynaphthalene-7-sulfonic acid bound in 6-position to alkaline aqueous dyestufi composition which contains the the azo linkage, 1:2-di(,B-hydroxyethylamino)-ethane, and complex copper compound of the dyestufi of the formula OH HO OH HO H|N IE H018 N H;

anions of pyrophosphoric acid, said composition contain- '1:2di-(B-hydroxyethylamino)ethane, and sodium pyroing copper in combined form, said copper being present in phosphate. alkali-resistant combination. 40 14. Process for coloring cellulosic textile materials with 10. Process for coloring cellulosic textile materials with metalliferous azo dyestutis sparingly soluble in water, metalliferous azo dyestufis sparingly soluble in water, which comprises applying to said materials a neutral to which comprises applying to said materials a neutral to alkaline aqueous dyestufl composition which contains the alkaline aqueous dyestuif composition which contains a complex nickel compound of the dyestufi of the formula (I)H H0 0 H H0 HQN 01H H015 NH:

dyestutf of the formula l:2di-(fl-hydroxyethylamino)-ethane, and sodium pyro- HO phosphate.

I 15. Process for coloring cellulosic textile materials with O metalliferous azo dyestuffs sparingly soluble in water,

which comprises applying to said materials a neutral to wherein each R represents the radical of a 2-amino-5-hyalkaline aqueous dyestutf composition which contains the droxynaphthalene-7-sulfonic acid bound in 6-position to complex copper compound of the dyestutf of the formula the azo linkage, 1:2-di-(p-hydroxyethylamino)-ethane, and

anions of pyrophosphoric acid, said composition contain- 1:Z-di-(fl-hydroxyethylamino)-ethane, and sodium pyroing nickel in combined form, said nickel being present in 7 h h alkali'reslstant combmailon 16. Process for coloring cellulosic textile materials with 11. Process for coloring cellulosic textile materials with metalliferous azo dyestufis sparingly soluble in Water, metalliferous azo dyestuffs sparingly soluble in Water,

which comprises applying to said materials a neutral to which Comprises pp y to said materials a neutral to alkaline aqueous dyestuff composition which contains the complex nickel compound of the dyestutf of the formula HO-CHr-OHg-HN S 01H 1:2-di-(fi-hydroxyethylamino)-eth.ane, and sodium pyrophosphate.

I7. A neutral to alkaline aqueous azo-dyestuff composition suitable for being applied on cellulosic textile materials, which contains a dyestutf containing at least two azo linkages and being capable of forming metal compounds sparingly soluble in Water, an aliphatic amine corresponding to the formula in which R1 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having at most three carbon atoms, and a hydroxymethyl group, R2 represents a member selected from the group consisting of a hydrogen atom and a methyl group, and n represents a whole number of at the most 4, and anions of a phosphoric acid containing at least two phosphorus atoms in the acid molecule, said composition containing in combined form a metal having an atomic number from 27 to 29, said metal being present in alkali-resistant combination.

18. A dyestutf preparation suitable for being applied on cellulosic textile materials, which contains a dyestull containing at least two azo linkages and being capable of forming metal compound sparingly soluble in Water, an aliphatic amine corresponding to the formula in which R1 represents a member selected from the group consisting of a hydrogen atom, an alkyl group having at most three carbon atoms, and a hydroxymethyl group, R2 represents a member selected from the group consisting of a hydrogen atom and a methyl group, and )1 represents a Whole number of at the most 4 anions of a phosphoric acid containing at least two phosphorus atoms in the acid molecule, said composition containing in combined form a metal having an atomic number from 27 to 29, said metal being present in alkali'rcsistant combination.

References Cited in the file of this patent UNITED STATES PATENTS 2,071,385 Bell Feb. 23, 1937 2,594,803 Riat Apr. 28, 1952 2,662,906 Menzi Dec. 15, 1953 FOREIGN PATENTS 676,584 Great Britain July 30, 1952 169,324- Austria Nov. 10, 1951 OTHER REFERENCES Jour. Soc. Dyers and Colorists for November 1946,

pages XVI (advertisement). 

1. PROCESS FOR COLORING CELLULOSIC TEXILE MATERIALS WITH METALLIFEROUS AZO-DYESTUFFS SPARINGLY SOLUBLE IN WATER, WHICH COMPRISES APPLYING TO SAID MATERIALS A NEUTRAL TO ALKALINE AQUEOUS DYESTUFF COMPOSITION WHICH CONTAINS A DYESTUFF CONTAINING AT LEAST TWO AZO LINKAGES AND BEING CAPABLE OF FORMING METAL COMPOUNDS SPARINGLY SOLUBLE IN WATER, AND ALIPHATIC AMINE CORRESPONDING TO THE FORMULA 